CN102214735A - Method for preparing absorbed layer of CIGS (copper indium gallium selenide)/sulfur solar cell - Google Patents
Method for preparing absorbed layer of CIGS (copper indium gallium selenide)/sulfur solar cell Download PDFInfo
- Publication number
- CN102214735A CN102214735A CN2011101559885A CN201110155988A CN102214735A CN 102214735 A CN102214735 A CN 102214735A CN 2011101559885 A CN2011101559885 A CN 2011101559885A CN 201110155988 A CN201110155988 A CN 201110155988A CN 102214735 A CN102214735 A CN 102214735A
- Authority
- CN
- China
- Prior art keywords
- indium gallium
- copper indium
- gallium selenide
- film
- sulfur
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Photovoltaic Devices (AREA)
- Physical Vapour Deposition (AREA)
- Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
Abstract
The invention relates to a method for preparing an absorbed layer of a CIGS (copper indium gallium selenide)/sulfur solar cell. The method is characterized by comprising the following steps: firstly, depositing a conducting film of a bottom layer on a substrate; and preparing a CIGS/sulfur thin film on the conducting film of the bottom layer, wherein the CIGS/sulfur thin film on the conducting film of the bottom layer is formed by taking argon as a sputtering gas and a CIGS/sulfur alloy target as a target material, and adopting a DC (direct current) pulse magnetron sputtering method. The method has the beneficial effects that: 1, the preparing process is finished in a vacuum state and the substrate is not exposed out of air, thus providing a good environmental basis for preparing excellent thin film; 2, hydrogen selenide/sulphur and other toxic gases are not used, thus improving the safety of coating films; and 3, the DC pulse magnetron sputtering method is used to prepare CIGS/sulfur so as to obtain the thin film with high compactness and uniformity and be easy to realize continuous production.
Description
Technical field
The present invention relates to the preparation method of a kind of Copper Indium Gallium Selenide/sulfur solar energy absorbed layer, belong to the photoelectric material new energy field.
Background technology
Copper Indium Gallium Selenide (Cu (In, Ga) Se
2Abbreviation CIGS) thin film solar cell is considered to the most promising solar cell of a new generation, the copper indium diselenide of yellow copper structure (CIS) or to mix Copper Indium Gallium Selenide (CIGS) compound that gallium forms be the direct band gap material is considered to the most promising solar cell with its solar cell as absorbed layer.Since the nineties in 20th century, the Copper Indium Gallium Selenide battery is the highest hull cell of conversion efficiency in hull cell.In August, 2010, it is 20.3% that the Copper Indium Gallium Selenide solar cell that Germany solar energy and hydrogen research center (ZSW) make refreshes the high conversion efficiency in laboratory, this record is reduced into 0.1% with the gap of the efficient of Copper Indium Gallium Selenide and polycrystalline silicon solar cell, and the Copper Indium Gallium Selenide solar cell has also that cost is low, and the life-span is long, and the low light level is good, radioresistance, absorption bands is wide, can flexibility etc. many-sided advantage, as seen very big development prospect is arranged.
The structure of Copper Indium Gallium Selenide solar cell is generally: substrate/metal back electrode/light absorbing zone (Copper Indium Gallium Selenide layer)/transition zone/Window layer/transparent electrode layer, the preparation of Copper Indium Gallium Selenide light absorbing zone is the core process of CIGS thin-film solar cell.
Copper Indium Gallium Selenide optical absorbing layer film preparation technology mainly contains two kinds: first kind is coevaporation, and it is Cu, In, Ga and Se to be done the source react coevaporation in vacuum chamber, or binary substep coevaporations such as Cu+Se, In+Se, Ga+Se; Second kind is the method for selenizing behind the metal initialization layer.The characteristics of coevaporation method are that the crystal grain of film is big, realize the Gradient distribution of element easily, the conversion efficiency height of battery, but this method to the equipment requirements strictness, evaporation process be not easy control, large tracts of land and serialization production difficulty are big; Second class methods are elder generation's proportional quantity deposition Cu, In, Ga metal initialization layers (comprising its alloy) by chemical formula on substrate, carry out selenylation reaction at the indoor and saturated selenium steam of vacuum heat again, final Copper Indium Gallium Selenide (Cu (In, Ga) Se that satisfies stoicheiometry that generate
2) semiconductor polycrystal film.
Because the selenium element is a rare element in the Copper Indium Gallium Selenide solar cell, replace selenium little with sulphur,, use sulfur selenium equally so replace selenium also by extensive studies with sulphur to the effectiveness affects of battery, also can carry out vulcanization reaction and generate copper indium gallium sulphur (Cu (In, Ga) S that satisfies stoicheiometry
2) semiconductor polycrystal film.The film-forming process of the preparation of metal initialization layer is comparative maturity, and the method for selenizing mainly contains two kinds, and the one, the substrate that deposited the metal initialization layer is put into the vacuum heat chamber, feed H during to uniform temperature
2Se (H
2Se+Ar) gas, the selenium atom that decomposes progressively generates the copper-indium-gallium-selenium semiconductor film material with the reaction of metal initialization layer, and the gas of feeding is changed make H
2S(H
2S+Ar) also can be made into the copper indium gallium sulphur semiconductor film material; Another kind method is to solid-state selenium source evaporation in thermal chamber, make selenium atom and initialization layer metal generation chemical reaction, progressively be transformed into copper-indium-gallium-selenium semiconductor film, solid-state selenium source changed do the sulphur source and also can be made into the copper indium gallium sulphur semiconductor film material, follow-up selenium (sulphur) change process is comparatively harsh and complicated to technology, wayward, and H
2Se (H
2S) poisonous, can exist potential safety hazard aborning.
Summary of the invention
Purpose of the present invention is exactly the uppity defective of process engineering that has preparation Copper Indium Gallium Selenide optical absorbing layer film now in order to overcome, and the preparation method of a kind of Copper Indium Gallium Selenide/sulfur solar energy absorbed layer is provided.
The technical solution adopted for the present invention to solve the technical problems is:
The preparation method of a kind of Copper Indium Gallium Selenide/sulfur solar energy absorbed layer, it is characterized in that: at first on substrate, deposit the bottom conducting film, on the bottom conducting film, prepare Copper Indium Gallium Selenide/sulphur film then, after Copper Indium Gallium Selenide/the sulphur thin film deposition forms, being placed into thermal chamber heat-treats, described Copper Indium Gallium Selenide/sulphur the film for preparing on the bottom conducting film is to be sputter gas with the argon gas, is target with Copper Indium Gallium Selenide/sulphur alloys target, and method by the DC pulse magnetron sputtering deposits formation.
On the basis of above-mentioned main technical schemes, can increase following further perfect technical scheme:
The frequency of described DC pulse magnetron sputtering is 50-250Hz.
Described DC pulse magnetron sputtering pulse duration is 320-1600ns.
Described deposition bottom conducting film and all under vacuum condition, carry out preparing Copper Indium Gallium Selenide/sulphur film on the bottom conducting film.
The vacuum degree of described DC pulse magnetron sputtering is 4 * 10
-1-8 * 10
-1Pa.
Described heat treatment is carried out under the low vacuum condition.
Described heat treatment is to carry out under 550 ℃ temperature.
The thickness of described Copper Indium Gallium Selenide/sulphur film is about 1.5 μ m.
Described is that method by magnetron sputtering deposit Mo formation on substrate at deposition bottom conducting film on the substrate.
The invention has the beneficial effects as follows that 1. preparation process is all finished under vacuum state, substrate is not exposed to atmosphere, for the film of preparing high-quality provides good environmental basis; 2. toxic gases such as use hydrogen selenide/sulphur have been avoided, the fail safe that has improved plated film; 3. adopt the method for DC pulse magnetron sputtering to prepare the film that Copper Indium Gallium Selenide/sulphur can obtain high compactness and high evenness, and realize easily producing continuously.
Embodiment
The preparation method of a kind of Copper Indium Gallium Selenide of the present invention/sulfur solar energy absorbed layer may further comprise the steps:
Preparation bottom conducting film: the vacuum degree with all sputtering chambers is extracted into required base vacuum degree 1 * 10 earlier
-5Pa opens the family of power and influence, and the soda-lime glass after cleaning is sent into upstream chamber, upstream chamber is vacuumized, when the vacuum degree of the vacuum degree of upstream chamber and coating chamber is suitable, open the family of power and influence glass is sent to coating chamber, utilize magnetron sputtering to make the metal conductive film Mo of bottom.
Preparation Copper Indium Gallium Selenide/sulphur film: the substrate that will deposit Mo is through the family of power and influence, Transition Room, and the family of power and influence is sent to coating chamber, regulates the flow of coating chamber argon gas and the pumping speed of vacuum pump and makes sputtering pressure remain on 4 * 10
-1-8 * 10
-1Between the Pa, preferred air pressure remains on 6 * 10
-1Pa, regulate the DC pulse frequency and the width of power supply, FREQUENCY CONTROL is between 50-250Hz, optimized frequency is controlled at 150Hz, pulse duration is controlled between the 320-1600ns, and the preferred pulse width is controlled at 1000ns, is sputter gas with the argon gas, with Copper Indium Gallium Selenide/sulphur alloys target is target, utilizes DC pulse sputter CIGS thin-film material.
Heat treatment: the substrate that will deposit copper indium gallium/sulphur thin-film material is through the family of power and influence; Transition Room; the family of power and influence; be sent to thermal chamber; thermal chamber is low vacuum state and nitrogen protection is arranged; heat treatment temperature obtains the absorbed layer of Copper Indium Gallium Selenide/sulfur solar energy at last at 550 ℃, and the thickness of described Copper Indium Gallium Selenide/sulphur film is about 1.4-1.6 μ m.
Claims (9)
1. the preparation method of Copper Indium Gallium Selenide/sulfur solar energy absorbed layer, it is characterized in that: at first on substrate, deposit the bottom conducting film, on the bottom conducting film, prepare Copper Indium Gallium Selenide/sulphur film then, after Copper Indium Gallium Selenide/the sulphur thin film deposition forms, being placed into thermal chamber heat-treats, described Copper Indium Gallium Selenide/sulphur the film for preparing on the bottom conducting film is to be sputter gas with the argon gas, is target with Copper Indium Gallium Selenide/sulphur alloys target, and method by the DC pulse magnetron sputtering deposits formation.
2. the preparation method of a kind of Copper Indium Gallium Selenide according to claim 1/sulfur solar energy absorbed layer is characterized in that: the frequency of described DC pulse magnetron sputtering is 50-250Hz.
3. the preparation method of a kind of Copper Indium Gallium Selenide according to claim 1 and 2/sulfur solar energy absorbed layer is characterized in that: described DC pulse magnetron sputtering pulse duration is 320-1600ns.
4. the preparation method of a kind of Copper Indium Gallium Selenide according to claim 1/sulfur solar energy absorbed layer is characterized in that: described deposition bottom conducting film and all carry out under vacuum condition preparing Copper Indium Gallium Selenide/sulphur film on the bottom conducting film.
5. the preparation method of a kind of Copper Indium Gallium Selenide according to claim 4/sulfur solar energy absorbed layer is characterized in that: the vacuum degree of described DC pulse magnetron sputtering is 4 * 10
-1-8 * 10
-1Pa.
6. the preparation method of a kind of Copper Indium Gallium Selenide according to claim 1/sulfur solar energy absorbed layer, it is characterized in that: described heat treatment is carried out under the low vacuum condition.
7. according to the preparation method of claim 1 or 6 described a kind of Copper Indium Gallium Selenide/sulfur solar energy absorbed layers, it is characterized in that: described heat treatment is to carry out under 550 ℃ temperature.
8. the preparation method of a kind of Copper Indium Gallium Selenide according to claim 1/sulfur solar energy absorbed layer is characterized in that: the thickness of described Copper Indium Gallium Selenide/sulphur film is 1.4-1.6 μ m.
9. the preparation method of a kind of Copper Indium Gallium Selenide according to claim 1/sulfur solar energy absorbed layer is characterized in that: described is that method by magnetron sputtering deposit Mo formation on substrate at deposition bottom conducting film on the substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101559885A CN102214735A (en) | 2011-06-11 | 2011-06-11 | Method for preparing absorbed layer of CIGS (copper indium gallium selenide)/sulfur solar cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101559885A CN102214735A (en) | 2011-06-11 | 2011-06-11 | Method for preparing absorbed layer of CIGS (copper indium gallium selenide)/sulfur solar cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102214735A true CN102214735A (en) | 2011-10-12 |
Family
ID=44745957
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011101559885A Pending CN102214735A (en) | 2011-06-11 | 2011-06-11 | Method for preparing absorbed layer of CIGS (copper indium gallium selenide)/sulfur solar cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102214735A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103779438A (en) * | 2012-10-22 | 2014-05-07 | 中物院成都科学技术发展中心 | Method for preparing CuInxGaySez prefabricated layer by electrochemical deposition |
| WO2020057484A1 (en) * | 2018-09-22 | 2020-03-26 | (Cnbm) Bengbu Design & Research Institute For Glass Industry Co., Ltd | Method for post-treating an absorber layer |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1367536A (en) * | 2002-03-08 | 2002-09-04 | 清华大学 | Copper-indium-galliun-selenium film solar cell and its preparation method |
| US20050006221A1 (en) * | 2001-07-06 | 2005-01-13 | Nobuyoshi Takeuchi | Method for forming light-absorbing layer |
| CN1719626A (en) * | 2005-06-03 | 2006-01-11 | 清华大学 | Cu-Ga alloy target for Cu-In-Ga-Se film solar battery and preparing process thereof |
| CN101260513A (en) * | 2008-04-23 | 2008-09-10 | 王东生 | Solar energy battery copper-indium-gallium-selenium film key target material and preparation method thereof |
| CN101728461A (en) * | 2009-11-06 | 2010-06-09 | 清华大学 | Method for preparing absorbing layer of thin film solar cell |
| CN101752451A (en) * | 2008-11-28 | 2010-06-23 | 中国电子科技集团公司第十八研究所 | Method for preparing absorption layer of thin film solar cell |
-
2011
- 2011-06-11 CN CN2011101559885A patent/CN102214735A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050006221A1 (en) * | 2001-07-06 | 2005-01-13 | Nobuyoshi Takeuchi | Method for forming light-absorbing layer |
| CN1367536A (en) * | 2002-03-08 | 2002-09-04 | 清华大学 | Copper-indium-galliun-selenium film solar cell and its preparation method |
| CN1719626A (en) * | 2005-06-03 | 2006-01-11 | 清华大学 | Cu-Ga alloy target for Cu-In-Ga-Se film solar battery and preparing process thereof |
| CN101260513A (en) * | 2008-04-23 | 2008-09-10 | 王东生 | Solar energy battery copper-indium-gallium-selenium film key target material and preparation method thereof |
| CN101752451A (en) * | 2008-11-28 | 2010-06-23 | 中国电子科技集团公司第十八研究所 | Method for preparing absorption layer of thin film solar cell |
| CN101728461A (en) * | 2009-11-06 | 2010-06-09 | 清华大学 | Method for preparing absorbing layer of thin film solar cell |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103779438A (en) * | 2012-10-22 | 2014-05-07 | 中物院成都科学技术发展中心 | Method for preparing CuInxGaySez prefabricated layer by electrochemical deposition |
| CN103779438B (en) * | 2012-10-22 | 2016-10-26 | 中物院成都科学技术发展中心 | A kind of electrochemical deposition prepares the method for CIGS preformed layer |
| WO2020057484A1 (en) * | 2018-09-22 | 2020-03-26 | (Cnbm) Bengbu Design & Research Institute For Glass Industry Co., Ltd | Method for post-treating an absorber layer |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101728461B (en) | Method for preparing absorbing layer of thin film solar cell | |
| CN102254998B (en) | Cadmium-free CuInGaSe thin film solar cell assembly and preparing method of zinc sulfide buffer layer thin film thereof | |
| CN106917068A (en) | Solar battery obsorbing layer Sb is prepared based on magnetron sputtering and rear selenizing2Se3The method of film | |
| CN102185024B (en) | Selenylation furnace for treating and preparing CIGS (Copper Indium Gallium Diselenide) solar cell absorbing layer and manufacturing method thereof | |
| CN107871795A (en) | A kind of regulation and control method of the band gap gradient of the cadmium doping copper zinc tin sulfur selenium film based on flexible molybdenum substrate | |
| CN107829071B (en) | The preparation method of copper antimony sulphur thin-film material | |
| CN101982567A (en) | Preparation method of copper indium selenium sulphur (CuInSe2-xSx) film for solar battery | |
| CN102270699A (en) | Preparation methods of CIGS (Cu (In, Ga) Se2)-free thin film solar cell and zinc sulfide buffer layer | |
| CN102153288A (en) | Method for preparing copper disulfide thin film with preferred orientation | |
| CN102751387B (en) | Preparation method of Cu (In, ga) Se2thin film for absorption layer of thin film solar cell | |
| CN104319298A (en) | Flexible substrate CdTe thin-film solar cell and preparing method thereof | |
| CN102214737A (en) | Preparation method of compound thin film for solar battery | |
| WO2014030412A1 (en) | Compound solar cell and method for manufacturing same | |
| KR101582200B1 (en) | A method for preparing CZTS thin film for solar cell | |
| CN105047750A (en) | Method for increasing conversion efficiency of thin-film solar cell | |
| CN102142484A (en) | Polysilicon/Cu (In, Ga) Se2 laminated cell process | |
| CN102214735A (en) | Method for preparing absorbed layer of CIGS (copper indium gallium selenide)/sulfur solar cell | |
| CN112259620A (en) | Sb2Se3Thin film solar cell and preparation method thereof | |
| CN108231925B (en) | A kind of preparation method of efficient CIS/CIGS solar battery | |
| Abouabassi et al. | Investigation on electrochemical deposition of Sb2Se3 thin films in aqueous acidic medium | |
| CN103194726A (en) | Preparation process of cuprum-indium-gallium-selenium film | |
| CN105633212B (en) | It is a kind of to be based on the method and apparatus that a step coevaporation technique prepares gradient band gap light absorbing zone | |
| CN104051577A (en) | Manufacturing method capable of improving crystallization property of copper zinc tin sulfur film of solar cell absorption layer | |
| KR101237466B1 (en) | Device for forming light absorbing layer by selenization | |
| CN105932093B (en) | A kind of preparation method of high quality CIGS thin film solar battery obsorbing layer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20111012 |